Method of separating the constituents of gaseous mixtures



March 31, 1 9.36. w w mso m- AL 2,035,516

METHOD OF SEPARATING THE CONSTITUENTS OF'GASEOUS MIXTURES Filed Aug. 1, 1934 ix/w/smv ENG/IVE i/a t 72 2d 4) INVENTOR BYM (AM uefiw wvf w THEIR ATTQRNEY$ Patented Mar. 31,; 1936 UNITED STATES PATENT" OFFICE I METHOD OF SEPARATING THE CON8'IITU-- ENTS F GASEOUS DIIXTUBES Walter Wilkinson, Bye, N. Y., and Joseph L.

Schlitt, Darien, Conn., asalgnors to Air Reduction Company, Incorporated, New York, N. Y a

' corporation of New York Application August 1, 1934, Serial m. 131,95:

fscmm. (c1. sa -115.5)

This invention relates a method and ap-' paratus for separating and recovering trom a complex mixture 01' gaseous hydrocarbons, certain constituents such astho'se belonging to the ethylene series 01' hydrocarbons, Camu A mixture to which the process forming the subject matter of thep'resent application may be applied, is for example, one obtained by cracking petroleum by-product gases suchas methane, ethane,

"w ethylene and propane or by cracking the heavy liquid residues or crude oils obtained in the petroleum industry. The cracked gases to be treated in the following process will thus consist of hydrogen, methane, ethane, propane, butane,

-15 ethylene, propylene, butylene and amylene, with possible smallperce'ntages oi the higher members '0! both the aliphatic and ethylene series. Small amounts of nitrogen may also be present.

It will be apparent as the description proceeds go thatthe method forming the subject matter or this application accomplishes a very dimcult and novel result, that is, the separation of a complex,

' gaseous, hydrocarbon mixture into its constituents, practically all of the valuable ones of which 35 are obtained in a substantially pure condition. I The method is distinguished by the fact that various fractions containing a fewer number of constituents than the originalfmixture are separated from the original mixture and are then 30 completely separated in auxiliary apparatus. The products or these auxiliary separations which contain ethylene are thenreturned to the ethylene rectifier, The inventionis generally applicable to gaseous mixtures of varying constitu- '5 ents, but is particularly adaptable to the separa tion 01 oleflne hydrocarbons, ethylene and propylene from mixtures containing many other hydrocarbons gases, someoi which have boiling points higher than that of any desired constituent and 40 othrs of which have boiling points i e -1mm,

- W /a es ons m w a z hers or which hl boi ing, poi ts lvins etwe t m oi fthe desired lconstituents ig Mixtures :suoh ias';

those lmentionedcare pr duced byvf crackingf'r pr ofthepetroleumindustries. a: i'-= haye boiling points 'lying: between thef i volatile constituents -(hy1drog'en; andme 50 'thanei; and .1 thosexof the" more "condensible "co stituentsusuch as -butane, butyleneia'nd, heavie hydrocarbons or -both aliphatic "ethylen cuts are asiollows:

' e two constituents ethyleneaand ipropyl' e ing point of ethylene (-103" C.) and that of propylene (-4'l C.). 5

The primary object or the present invention is to recover in substantial purity and singly the first two of the'ethylene series constituents of a 5 mixture such as the one above indicated, namely, ethylene and propyiene, and to segregate the 7 higher members present, such as butylene and amylene, mixed only with heavier aliphatic hydrocarbons such as butane and pentane. 1

Another objector the invention is to provide an efllcient method oi producing the retrigerative eiifect necessary i'or the accomplishment oi the desired separation. r I

' 7 Other objects and advantages will be apparent as the invention isbetter understood by reference to the following specification and the accompanying drawingwhich illustrates diagrammatically w an apparatus suitable i'orthepractice or themvention, it being understood that the details of such apparatus, well known in the a'rt,;are omitted for the purpose-oi clarity andthat suitable apparatus ofvarying constructions can be employed to accomplish the p rp se of the invention. i

Y .25 The method. is designed to met-the pressing I need i'or a continuous commercial operatlon'which will separate the various oleflne hydrocarbons, particularly ethyleneand propylenefirom a complex mixture or hydrocarbons'such as is' obtained by cracking; petroleum hydrocarbons, either gaseousnor liquid, derived 'irom the pe-. troleumindu'stry. The result of cracking such hydrocarbon mixtures is to'obt'ain' a complex gaseous mixtureconslstlng of hydrogen, methane,

ethane, propane,butane, pentane, ethylene, pro- 7 pylene, butylene, amylene, etcwThese variou's hydrocarbonschave boiling points 'over a wide T range .01 variation. Thusat a 01- 1 atmosphere --thebciling points (it these c'onstitu- 40 s ac 2 .!!-r ;p9ntbne sass Secondary'pentane +2785 Normal pentane 4-36.06

. arated by the process about to be described, is as follows, the percentages being in mols.

Per cent, ydrogen (H2) 10 Methane (CH4) 30- Ethylene (C2H4) 30 Ethane (CrHe) 6 Propane (CaHa) 1 Propylene (CaHc) l4 Butylenes I 8 Amylene, pentane, benzol and toluol 1 The problem of the separation 01' thejdesired constituents, e. g., ethylene, propylene and butylene, from such a mixture is an exceedingly difficult one particularly in that not only does the mixture contain constituents of boiling points both higher and lower than those of any of these desired constituents, but it also contains components whose boiling points are. intermediate between those of any two desired constituents. For example, one such component, especially, is ethane, substantial quantities of which always occur in the gaseous mixtures resulting from cracking hydrocarbons either gaseous orliquid.

The difliculties encountered in attempting to separate the olefine hydrocarbons from such a complex mixtureby a single continuous process involving only partial liquefaction, evaporation and rectification, are very great for the reason that on account of the large number of constituents it is almost impossible to ensure a complete separation of any constituent by means of any preliminary partial liquefaction.

In beginning the experimental work upon the problem of separation it was realized that an important step would be accomplished if we were able to separate by partial liquefaction combined .with a preliminary high pressure rectification, the

incoming mixture into two portions, one of which would be free from ethylene and the other of which would be free from propylene. Our preliminary experiments were directed toward this 'end and in order to satisfactorily accomplish this result a special type of combined condenser and high pressure rectifier was developed. This part of the apparatus will be described later in the specification.

Furthermore there is the problem of producing the necessary refrigerative efiect to cause condensation of the various portions of the mixture which must be reduced to the liquid state preliminarily to the employment of the process of rectification. We were enabled to discover a sequence of steps such that the low temperature refrigeration necessary to be produced is obtained by the expansion in an expansionmachine of a hydrogen-methane uncondensed residue. This expansion takes place without liquid appearing in the expansion machine exhaust and with the removal of substantially all of the ethylene from the expanded fluid. These are two indications'of the long experimental campaign in which -we engaged during the development of this process. The method as a whole is characterized by the "feature that the separation is,-accomplished in a series of steps. The first step isto divide the incoming mixture into portions of varying volatility and temperature, each of which is subse quently'and continuously treated-in order to separate them completely into their constituents. For example, thefirst separation of the compressed incoming mixture consists in segregating by themselves all constituents of boiling points equal to or-higher than that of propylene, for example, butane, butylene, propane, propylene. From the remainder of the incoming mixture, which may still contain small percentages of propylene, is separated, as the second step, a portion containing the remainder of the propylene, a major portion of the ethane and a considerable portion of the ethylene. This fraction is then admitted to an intermediate level of a rectifier wherein it cascades over trays ofthe usual type. The remainder of the mixture, stillat the original pressure, consists mainly of hydrogen and methane and this enters an exchanger system wherein substantially all the remaining ethylene is liquefied out together with some methlane. The residual vapor passes to an expansion engine wherein its pressure is lowered to about one atmosphere with the performance of external work. The liquid mixtures of ethylene and methane are separated in an auxiliary rectifier into practically pure methane and a high ethylenebearing liquid, the latter passing thence to the main rectifier. The first separated fraction consisting of propylene and constituents of higher boiling point is separated in an auxiliary-rectification column as hereinafter described in detail. The invention will be described with reference to the separation of a typical composition or mixture hereinbei'ore described in apparatus illustrated in the drawing and suitable for the accomplishment of the intended purpose. It will be understood that such description is illustrativeand subject to modification in treating compositions or mixtures which may vary widely in the con,-

stitue'ntsand the proportions thereof present depending upon the source of the initial mixture and the previous treatment to which it may have been subjected. r

The mixture is supplied at an initial pressure sufiicient for the purpose, for example,

about pounds per square inch through an in-,

' equipped with hats H, to permit liquid to ilow downwardly and countercurrent to vapors arising'from such liquid, together with the gaseous mixture introduced through the pipe 1. The

gaseous mixture and accompanying vapors pass 'Iupwardiy through the trays It to the tubes I! of a condenser which is surrounded by liquid prodnets of a further separation hereinafter described. The resulting partial liquefaction and rectification of the liquids and vapors in section I of the column results in a separation of the initial gaseous mixture into two fractions. The liquid fraction which accumulates in the bottom of section 8 consists primarily of propylene and constituents boiling at higher temperatures, to-

gether with a small proportion of the ethane present in the initial gaseous mixture. This liquid is heated by supplying any suitable heating medium. preferably-at aboutroom' temperature, tothecoil II inorderto facilitateseparav I aosau-e 1 1 -'3 I as of ccnstituentsboilingat temperatureslower than the boiling point of propylene. The vapor fraction'rises through section [and assists. in the rectification of the descending liquid. The

liquid which accumulates in the bottom of sections is withdrawn through a pipe I and subiected to further treatment ashereinai'ter described.

A portion of the liquid condensed in the tubes l2 and consisting of approximately 70% ethylene.

the remainder being principally ethane and composition. One-of these liquid fractions containfuall of the propylene present in the initial 'mix re. The other liquid fraction together with the vapor fraction contain all of the ethylene. These desirable constituents are-separated from contaminating impurities by th uncondensed residue consisting principally of hydrogen-and methane but containing ;a small "amount of ethylene is delivered through a pipe 20 to an exchanger 2| wherein it is subjected to the cooling eflect of the expansion, in-expansion engine 21, of the hydrogen and m thane residue,

, together with a portion, if desirab e, of the emucut of'column 34. Thus in the exchanger 2! the ethylene constituent is liquefied together with some methane and leaves through a pipell.

The balance of the residue passes'through a pipe 23 to another section '24 of the exchanger 2|;

engine 21.

wherein its temperature is raised, and thence through a pipe 25 and valve to'an expansion,

A pipe It delivers the expan product to a section I! of the exchanger II where it gives up a portion of its cold to'the gases in the section lid. The residue'consisting of'hydrogen and methane isdelivered then' through a pipe 30 for further use as hereinafter described.

- The liquid from the trough ll passes through,

the pipe I! to an exchanger II and thence through a pipe 32 and valve)! to the lowest section of an auxiliary column 34 which is provided with theusual trays Ii, equipped with hats 80. to facilitate rectification of liquids and vapors .passin; through the column. The liquid 1mm me tubes II is delivered by the pipe ll through a valve 31 to an intermediate section of the. column 34. The liquid from the exchanger II is delivered by the pipe 22 through a valve II also to an intermediate section of the: column 34. The rectiflcation is completed in the column 34 by supplying liquid methane to the top thereof. To accomplish this purpose and to afford additional refrigeration. a portion'of the'eiiluent from the column 34 escaping through the pipe 10 is delivered through a pipe 4! to anexchangerll and passes thence through apipe l2 and exchanger to a compressor 44 where it is reeompressedv to a relatively high pressure; fofx'ample 500 pounds per square inch. The compressed gas returning through a pipe II and the exchanger ll is delivered by a pipe to a coil ll auxiliary column immersed in liquid ll: thence through a pipe I. and exchanger ll throughavalve lltotheuppei'endofthecole umn u. The reflux liquid thusprovided washes ethylene and ethane from the gasesrisingin the column, so that'the eilluent escaping throughthe pipe ll consists principally of methane. The portion which is not recycled in the manner described passes through a valve" to exchanger 2| wherein it assists in producing liquidin sec- The auxiliary rectification aii'ords a supply of liquid consisting principally of ethyleneand ethane which is delivered through an' inlet ii to the column 0 at about the level oi the condenser tubes II and accumulates around such-tubes.

. being vaporized by heat exchange with the gases within the tubes.

To afford a'reflux of substantially-pure ethyltion lie and escapes through the pipe ll hereinbeiore described.

one, the eiiiuent from the column I is delivered through the pipe I! to an exchanger 53 and thence through a pipe 84 to an exchanger II. it passes thence through pipe 56, exchanger 51. pipe I, exchanger 5! and pipe 00 ton compressor ll wherein a portion of the eilluent is recompressed to a relatively high pressure, for example, 160 to 1000 pounds-per square inch. 'Apart of the ethylene which is one of the desired'products of the separation is withdrawn through a pipe 0! and valve 03. The portion which is recompressed is delivered through a pipe 64, exchanger II and pipe 00 to a coil 06 in the bottom of, an 61, hereinafter described whereinit is cooled and returns through a pipe 08 to the exchanger 51 and thence through a pipe 00 to a coil 10 immersed in liquid surrounding the tubes 12 wherein it is cooled. The fluid. is then conveyed through a pipe II to the exchanger and thence through a pipe 12 and valve 13 to the top of the column s. The pure ethylene liquid reflux thus provided flows downwardly over trays ll provided withthe usual hats l0 and washes from the rising vapors the ethane constituentof such vapors, so that the liquid accumulating around the tubes l2 at the lower end of the column [consists of ethylene and ethane, the latter constituent being in excess. Pure ethylene, as hereinbefore indicated, is withdrawn as the eiiluent of the rectification in the column], and thus oneof the desired confstituents is separated from theinitial gaseous mixture substantially free from contaminating constituents.

As hereinbefore indicated, the propylene conthe top. 'The residual liquid passesthrough a' valve II and pipe I! into a second rectification column I; having-trays l4 and hats I} and being provided at its lower end with a coil 00 which may be supplied with any suitable heating medium.

The vapor from the liquid returns to the column 01 through a pipe II. The residualliquid escapes through a valve II and pipe II to the exchanger 6 and thence is withdrawn. This fraction will consist of butylene,' butane, and any other constituents present, the boiling points of which are higher than that of butyle'ne.

A portion of the vapors rising through the column 61 is diverted into an auxiliary rectification column 90 and condenser tubes 92, around which the cold gases from the'pipe 30, consisting of hydrogen and methane, circulate to liquefy the more readily condensible constituents of the rising vapors. The cooling medium escapes through a pipe 93 to the exchanger 16 and thence through a pipe 94 to the exchanger 6, being withdrawn as a mixture of methane and hydrogen. The effluent from the auxiliary column 90 consists of propylene and is withdrawn through a pipe 95 and valve 96 to the exchanger 16 and thence through a pipe 91 to the exchanger 6. The propylene is withdrawn as a substantially pure pr oduct and one of the desirable recovered constituents.

The remaining vapor rising through the column 61 enters tubes 98 .of a condenser which is surrounded by liquid and/or vapor supplied from the column 9 through pipes 09 and I controlled by valves IM and I02. The cooling agent escapes through a pipe I03 controlled byvalve I04 to a with a purge'valve NM. The pipe I05 deliversthese products to the exchanger I6, whence they escape through a pipe I08. At this point they are mixed with the impure propane vapors issuing rom an intermediate level of rectifier 83. The combined vapors pass through pipe I00 to exchanger 6 and are withdrawn therefrom as a mixture of propane and ethane.

Thus, as described, the initial mixture is separated by a succession of steps, of which the first is the important one of splitting the gaseous mixture into two fractions, one of which contains substantially all of the propylene, and the other of which contains substantially all of the ethylene, with further steps to separate the various impurities from the ethylene and the propylene. the desired constituents of the gaseous mixture. These constituents are recovered in substantial purity. Methane and hydrogen 'are withdrawn together, as are also propane and ethane, and butane and butylene, together-with other constituents boiling at higher temperatures.

A particular advantage of the method as described is the avoidance of external refrigeration, the application of which would involve very considerable difficulty in the successful separation of the desired constituents. The most important features of this process in respect to the method of refrigeration are two in number. (1) The necessary refrigeration at the cold end of the system is obtained by means of expansion of all the unconsensed residues in the system in an expansion machine with external work. (2) The reents designed tobe separated thereby are not present in the initial gaseous mixture.

The expression "rectifier with the usual trays and hats" should be interpreted throughout the specification to indicate any type of rectifier commonly used in industry.

Various changes may be made, therefore, in the procedure and in the apparatus utilized therefor without departing from the invention or sacrificing any of the advantages thereof.

We claim:

l. The method of recovering ethylene and probyleneseparately and in substantial purity from complex gaseous mixtures containing these constituents and including methane, ethane and propane which comprises separating from the compressed gaseous mixture by liquefaction at the same pressure liquid fractions, one of which includes substantially all'of the propylene and the o.her the major portion of the ethylene, and thereafter rectifying the liquid fractions to separate the desired constituents from other eonstituents of such fractions.

2. The method of recovering ethylene and propylene separately and in substantial purity from complex gaseous mixtures containing these constituents and including methane, ethane and propane which comprises separating from the compressed gaseous mixture by liquefaction at the same pressure liquid fractions, one of which includessubstantially all of the propylene and the other the major portion of the ethylene, and thereafter rectifying the liquid fractions to separate the desired constituents from other constituents of such fractions, and maintaining the refrigeration required for the separation by recompression of separated constituents, thereby avoiding external refrigeration.

3. The method of recovering ethylene and propylene separately and in substantial purity from complex gaseous mixtures containing these constituents and including methane, ethane and propane, which comprises separating from the compressed gaseous mixture by liquefaction at the same pressure liquid fractions, one of which 7 ing the gaseous residue and rectifying the liquid fractions to separate the desired constituents from the other constituents of such fractions.

4'. The method of recovering ethylene and propylene separately and in substantial purity from complex gaseous mixtures containing these constituents and including methane, ethane, and propane, which comprises separating from the compressed gaseous mixture by liquefaction at the same pressure liquid fractions, one of which includes substantially all of the propylene and the other the major portion of the ethylene, discarding the gaseous residue, rectifying the liquid fractions to separate the desired constituents from the other constituents of such fractions, and maintaining the refrigeration required for the separation by recompression of separated-constituents, thereby avoiding external refrigeration.

5. The method of recovering ethylene and propylene separately and in substantial purity from complex gaseous mixtures containing-these constituents andincluding methane, ethane, and propane, which comprises separating from the compressed gaseous mixture by liquefaction a plurality of liquid fractions, one of which includes substantially all of the propylene and the others substantially allof the ethylene, subjecting the ethylene fractionsto-an auxiliaryrectiflcation to separate constituents of lowerboiling point there-' from, and then to rectification from which the ethylene is withdrawn as the gaseous eiiluent.

6. The method of recovering ethylene and propylene separately and in substantial purity from complex gaseous'mixtm'es containing these constituents and including methane, ethane, and propane, which comprises separating from the compressed gaseous mixture by liquefaction a plurality of liquid fractions, one of which includes substantially all of the propylene and 'the others substantially all of the ethylene. subjecting the ethylene fractions to an auxiliary rectification to separate constituents of lower boiling point therefrom. and then torectification from which the ethylene is withdrawn as the gaseous eilluent, and treating the liquid propylene fraction to separate other constituents therefrom.

7; The method of recovering ethylene and propylene separately and in substantial purity 8. The method of recovering ethylene and propylene separately and in substantial purity from complex gaseous mixtures containing these constituents and including methane, ethane and propane, which comprises separating from the compressed gaseous mixture by liquefaction a plurality of liquid fractions. one of which includes substantially all of the propylene and the others substantially all of the ethylene, discarding the unliquefied residue, subjecting the ethylene fractions to an auxiliary rectification to separate constituents of lower boiling point therefrom and then to rectification from which the ethylene is withdrawn as. the gaseous eilluent, and treating the liquid propylene fraction to separate other constituents therefrom, I

9. The method of recovering ethylene and propylene separately and in substantial purity from complex gaseous mixtures containing these constituents and including methane,'ethane. and

propane, which comprises separating from. the compressed gaseous mixture by liquefaction a pluralityof liquid fractions, one of which includes substantially all of the propylene and the others substantially all of the ethylene, subjecting the ethylene fractions to an auxiliary rectification to separate constituents of lower boiling point therefrom, and then to rectification from which the ethylene is withdrawn as the gaseous efiluent, and maintaining the refrigeration required for the separationby recompression of separated constituents, thereby avoiding-external refrigeration.

a WALTER WILKINSON. JOSEPH L. SCHLITT.

. Certificate of Correction' Patent No. 2,035,516. Y March 31, 1 936.' WALTER WILKINSON ET AL. It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correctionas followsrPage 1, second column, line 26, for "metf read meet; line'52, for +9.5 read +1.0; and line 53, for +27.95 read +9.5; page 4, first column, line 62, .for unconsensed read uncMLdensed; and second column, lme 11, "cla m 1,'for fprobylene read propylene; and that the'said Letters' Patent should be read with these correetione therein that the same may conform to therecord of the case in the Patent Ofiice.

Signed and sealed this 28th day of April, A. n. 1936."

[m LESLIEF RAZER; 1

Acting of Patents, 

